Photoinduced Decarboxylative Amino‐Fluoroalkylation of Maleic Anhydride

Abstract

A photoinduced decarboxylative three‐component coupling reaction involving amine, maleic anhydride, and fluorinated alkyl iodides has been developed, leading to synthetically valuable fluoroalkyl‐containing acrylamides with a high E selectivity. A broad array of substrates including monoprotected amino acid are capable coupling partners. Preliminary mechanistic studies suggest a stepwise process. This reaction represents the first example of photoinduced decarboxylative difunctionalization of maleic anhydride.

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

“…Fluoroalkylated E ‐configured acrylamides can also be accessed from maleic anhydride and amines via tandem ring opening decarboxylative fluoroalkylation (Scheme 57). [186] The reaction proceeds under photoredox conditions employing Ru(bpy) 3 Cl 2 as a catalyst for the formation of fluoroalkyl radical (oxidative quenching with IR F ) and oxidative decarboxylation.…”

Promising reagents for difluoroalkylation

“…The photoinduced decarboxylative difunctionalization of maleic anhydride with amine and fluorinated alkyl iodides was reported by the Zhang group (Scheme 58). 131 A variety of fluorinated alkyl halides and amines reacted smoothly in this reaction. The difluoroalkyl radical which was generated from oxidative quenching reaction between fluorinated alkyl iodides and excited Ru(II)* was also possible in this reaction.…”

Single-Step Synthesis of γ-Ketoacids through a Photoredox-Catalyzed Dual Decarboxylative Coupling of α-Oxo Acids and Maleic Anhydrides

“…Again a single example with maleic anhydride was reported and a similar ring opened product was observed; however, decarboxylation did not occur in this case such that the maleic acid adduct was formed (Scheme c). In 2020, Zhang reported a decarboxylative amino-alkylation of maleic anhydrides by using anilines as the nucleophile to open maleic anhydride . Zhang observed that the second decarboxylation occurs via a radical process that reinstalls the olefin for the synthesis of acrylamides; similar olefin formation is not observed in our reaction.…”